Enantioselective Allylic Substitution of Morita-Baylis-Hillman Adducts Catalyzed by Chiral Bifunctional Ferrocenylphosphines

Article abstract of DOI:10.1002/ejoc.201600045

A series of air-stable chiral ferrocenylphosphines (LB1-LB4) were prepared and used in the asymmetric allylic substitution of Morita-Baylis-Hillman (MBH) adducts with phthalimide under mild reaction conditions; the (R,S_Fc)-ferrocenylphosphine LB4 afforded the desired amination products 3 in moderate yields with excellent enantioselectivities. The absolute configuration of 3o was confirmed by X-ray analysis.

Full text of DOI:10.1002/ejoc.201600045

DOI: 10.1002/ejoc.201600045
Full Paper
Asymmetric Catalysis
Enantioselective Allylic Substitution of Morita–Baylis–Hillman
Adducts Catalyzed by Chiral Bifunctional Ferrocenylphosphines
[
a]
[a]
[a]
[a]
[a]
Linglong Zhu, Haiwen Hu, Liang Qi, Yi Zheng, and Weihui Zhong*
Abstract: A series of air-stable chiral ferrocenylphosphines cenylphosphine LB4 afforded the desired amination products 3
LB1–LB4) were prepared and used in the asymmetric allylic in moderate yields with excellent enantioselectivities. The abso-
(
substitution of Morita–Baylis–Hillman (MBH) adducts with lute configuration of 3o was confirmed by X-ray analysis.
phthalimide under mild reaction conditions; the (R,S )-ferro-
Fc
Introduction
onates. In 2007, Hou and co-workers[6] reported the enantiose-
lective substitution of MBH adducts derived from acrylate with
The Morita–Baylis–Hillman (MBH) reaction has emerged as an phthalimide, catalyzed by planar chiral [2,2]-paracyclophane
attractive approach for the preparation of α-methylene-ꢀ- monophosphanes to give the allylic amination products with
hydroxycarbonyl compounds, which are versatile synthetic high regioselectivities but poor-to-moderate enantioselectivi-
[
1]
building blocks in organic synthesis. In recent decades, great ties (9–71 % ee); however, the absolute configuration of these
effort has been devoted to the synthesis of these chiral com- amination products was not disclosed (Scheme 1). Later, Shi
[
7,8]
pounds through the following two approaches: the asymmetric and co-workers
developed a set of highly active chiral phos-
[
2]
Morita–Baylis–Hillman (MBH) reaction and the asymmetric phane organocatalysts, containing both Lewis basic and Brön-
[
3]
substitution of MBH adducts. Owing to the broader range of sted acidic sites, which can achieve highly enantioselective all-
substrates, increasing attention has been paid to the asymmet- ylic amination of acetates of MBH alcohols derived from methyl
ric substitution of MBH adducts. Notably, great progress have vinyl ketone (MVK) or ethyl vinyl ketone (EVK) to afford the
been achieved in the organophosphine-catalyzed allylic amin- target products in good yields and up to 90 % ee (Scheme 2).
[
4]
ation and allylic alkylation of MBH acetates and carbonates.
To date, methodologies for the highly enantioselective substitu-
[
5]
In 2004, Krische and co-workers first reported the asymmetric tion of carbonates or acetates of MBH alcohols derived from
amination of MBH acetates with phthalimide catalyzed by chiral MVK and EVK have been well-established and can be achieved
phosphanes, which provided the corresponding substitution readily, but the asymmetric reactions of MBH adducts derived
products in good yields along with moderate ee values. Inspired from acrylate with phthalimide have remained a challenge.
by the elegant work of Krische, Hou and Shi independently Thus, the discovery of new catalysts to achieve the highly enan-
studied the asymmetric transformation of MBH adducts to build tioselective substitution of MBH acetates or carbonates derived
highly functionalized γ-butenolides from MBH acetates or carb- from acrylate is still a highly desirable goal. Very recently, our
Scheme 1. Previous work by Hou and co-workers.
[
a] Collaborative Innovation Center of Green Pharmaceutical Engineering,
College of Pharmaceutical Sciences, Zhejiang University of Technology,
Chao Wang Road 18th, 310014, Hangzhou, P. R. China
E-mail: weihuizhong@zjut.edu.cn
group reported a highly enantioselective [3+2] cycloaddition
reaction catalyzed by the chiral bifunctional ferrocenylphos-
[
9]
phine LB2 (Scheme 3). The catalysts containing five-mem-
bered heteroaryl rings and amide moieties presented higher
catalytic activities owing to a favorable steric interaction be-
www.zjut.edu.cn
Supporting information and ORCID(s) from the author(s) for this article are
available on the WWW under http://dx.doi.org/10.1002/ejoc.201600045.
Eur. J. Org. Chem. 2016, 2139–2144
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Full Paper
tween the diphenylphosphine and heteroaryl moieties. On the yield with 94 % ee (Table 1, Entry 4). A slight increase of both
basis of these results, in this work, we chose the best structural yield and ee was observed for a prolonged reaction time of
pattern and modified the five-membered heteroaryl ferrocenyl- 240 h (Table 1, Entry 5). Notably, decreased catalyst loadings
phosphine catalyst and then investigated if the highly enantio- and temperature had little influence on this reaction (Table 1,
selective amination of MBH adducts derived from acrylate with Entries 6–9). The further exploration of the effect of the solvent
phthalimide could be achieved (Figure 1).
suggested that CHCl can significantly promote the reaction to
3
afford the corresponding product 3a in 74 % yield and 96 % ee
(
Table 1, Entries 10–13).
Table 1. Screening of chiral phosphines for the allylic substitution of MBH
adduct 1a with phthalimide 2.[
a]
Scheme 2. Previous work by Shi and co-workers.
Entry
Catalyst
mol-%]
Time
[h]
T [°C]
Solvent
3a
[
Yield[b] [%] ee[c] [%]
1
2
3
4
5
6
7
8
9
LB1 (20)
LB2 (20)
LB3 (20)
LB4 (20)
LB4 (20)
LB4 (10)
LB4 (20)
LB4 (20)
LB4 (20)
LB4 (20)
LB4 (20)
LB4 (20)
LB4 (20)
120
120
120
120
240
120
240
120
120
120
120
120
120
r.t.
r.t.
r.t.
r.t.
r.t.
r.t.
0
40
40
r.t.
r.t.
r.t.
r.t.
THF
THF
THF
THF
THF
THF
THF
THF
64
65
58
73
74
52
42
75
74
42
34
74
53
–86
91
92
94
96
96
96
94
96
94
75
96
92
Scheme 3. Asymmetric [3+2] cycloaddition reaction catalyzed by ferrocenyl-
phosphines.
CHCl
CH Cl
Et
CHCl
toluene
3
10
11
12
13
2
2
2
O
3
[
(
a] Unless otherwise specified, the reactions were performed with 1a
0.5 mmol), 2 (1.5 mmol), and catalysts LB1–LB4 (0.1 mmol) in THF (2.5 mL)
at room temperature. [b] Isolated yield. [c] The ee was determined by HPLC
analysis with a chiral column.
With the optimal reaction conditions in hand (Table 1, En-
try 12), the scope of this reaction was then explored with a
series of MBH acetates 1 derived from acrylate in the reaction
with 2 (Table 2). A variety of substituted MBH adducts 1 bearing
electron-withdrawing or -donating groups on aromatic ring or
different ester groups on the side chain all proceeded smoothly
after 120 h to afford the corresponding products (3a–3p) in
moderate-to-good yields (up to 74 %) and excellent ee values
Figure 1. The structures of the chiral bifunctional ferrocenylphosphines.
(
up to 96 % ee). We found that the substrate derived from
Results and Discussion
methyl acrylate delivered a better result than the substrates
The initial assays were performed with MBH adduct 1a and derived from ethyl acrylate and butyl acrylate (Table 2, En-
phthalimide (2) in the presence of the chiral bifunctional ferro- tries 1–3). Notably, electron-withdrawing aromatic MBH adducts
cenylphosphines LB1–LB4 (Table 1). Pleasingly, the allylic amin- were more reactive than electron-donating ones (Table 2, En-
ation product 3a was obtained in 65 % yield and 91 % ee with tries 1, 11, 13, and 15). In addition, multisubstituted aromatic
LB2 (20 mol-%) as the catalyst in tetrahydrofuran (THF) at room rings (Table 2, Entries 12 and 16) also afforded the correspond-
temperature for 120 h (Table 1, Entry 2). In addition, LB1 as the ing products in moderate yields along with high ee values. Ow-
catalyst resulted in a decrease in both yield and enantioselectiv- ing to steric hindrance, the ortho-heterosubstituted MBH ad-
ity (Table 1, Entry 1). Catalyst LB3 was also effective for this ducts gave lower yields than those of meta- or para-substituted
reaction and afforded the desired product 3a in moderate yield products (Table 2, Entries 6–10). Notably, the ortho-nitro-substi-
but good ee (Table 1, Entry 3). Delightfully, the dichloro-substi- tuted MBH adduct could not undergo this reaction (Table 2,
tuted catalyst LB4 showed the best enantioselectivity in this Entry 4). A naphthyl group was tolerated in this reaction, and
reaction and afforded the corresponding product 3a in 73 % the corresponding product 3p was obtained in moderate yield
Eur. J. Org. Chem. 2016, 2139–2144
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2140
© 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Full Paper
and ee (Table 2, Entry 17). Unfortunately, for the aliphatic MBH acetate generates the intermediate I and an acetate ion. The
acetate, the product was not obtained even if the reaction was acetate ion engages in an acid–base equilibrium involving de-
performed at a higher temperature (40 or 60 °C) or with a protonation of the pronucleophile, as proposed by Krische. In
higher catalyst loading (Table 2, Entry 18). The absolute config- our case, the pK of the pronucleophile phthalimide (pKa
=
a
[
12]
[13]
uration of 3o was determined to be R by X-ray analysis (Fig- 8.3) is higher than that of acetic acid (pK = 4.8); therefore,
a
ure 2). Interestingly, the absolute configuration of most of prod- the acetate should not deprotonate the phthalimide. Thus, we
ucts 3 should be (+)-S according to their specific rotation propose that the phthalimide directly attacks the γ position of
(
Table 2).
the olefin from the Re face of the olefin owing to a steric
repulsion between the aromatic group of the catalyst and the
phthalimide to offer intermediate II, which undergoes deproto-
nation to afford the final product 3.
Table 2. Asymmetric allylic substitution reaction of MBH adducts with phthal-
imide catalyzed by LB4.
[
a]
Entry
R/R1
4-NO
4-NO
4-NO
2-NO
4-FC
2-ClC
3-ClC
4-ClC
4-BrC
3-BrC
4-MeC
3,4-Me
4-MeOC
/Me
CC
2,4-Cl
Yield[b] [%]
ee[c] [%] Absolute configuration
1
2
3
4
5
6
7
8
9
2
C
C H
2 6 4
6
H
4
/Me
/Et
/nBu
74 (3a)
65 (3b)
60 (3c)
–
96
72
73
–
(–)-S
(+)-S
(–)-S
–
2 6
C
H
4
H
4
/Me
2 6
C
/Me
Scheme 4. Possible mechanism.
6
H
4
39 (3d)
35 (3e)
36 (3f)
51 (3g)
46 (3h)
41 (3i)
56 (3j)
36 (3k)
41 (3l)
46 (3m)
71 (3n)
57 (3o)
31 (3p)
Trace
72
90
82
75
73
89
73
91
62
92
89
94
78
–
(+)-S
(–)-R
(+)-S
(+)-S
(+)-S
(+)-S
(+)-S
(+)-S
(+)-S
(+)-S
(+)-S
(–)-R
(+)-S
–
6
H
4
/Me
/Me
/Me
6 4
H
H
6 4
6
H
4
/Me
/Me
Conclusions
10
11
12
13
14
15
16
17
18
6 4
H
6
H
4
/Me
/Me
/Me
We have developed a series of chiral ferrocenylphosphines to
promote the enantioselective allylic substitution of MBH ad-
ducts with phthalimide, and the chiral ferrocenylphosphine LB4
showed good catalytic activity for this reaction. Furthermore,
2
C
6
H
3
6
H
4
6 5
C H
4-F
3
6
H
4
/Me
/Me
[
14]
2
C
6
H
3
LB4 is reasonably air-stable in solution and in the solid state.
1-naphthyl/Me
phenylpropyl/Me
Efforts are in progress to use the chiral ferrocenylphosphine
catalysts for other asymmetric reactions.
[
a] Unless otherwise specified, the reactions were performed with
1
(
0.5 mmol), 2 (1.5 mmol), and LB4 (0.1 mmol) in CHCl (2.5 mL) at room
3
temperature. [b] Isolated yield. [c] The ee was determined by HPLC analysis
with a chiral column.
Experimental Section
Materials and General Experimental Details: All starting materials
were commercially available and used without further purification.
Melting points were determined with a Büchi B-540 capillary melt-
ing-point apparatus. Optical rotations were determined with an Au-
topol V polarimeter. The 1H and C NMR spectra of samples in
CDCl3 were recorded with a Varian-400 spectrometer at 400 and
13
100 MHz with tetramethylsilane (TMS, δ = 0 ppm) as an internal
standard. The chemical shifts are reported in ppm, and coupling
constants J are expressed in Hertz. The 31P NMR spectra of samples
in CDCl3 with 85 % H PO as an internal standard were recorded
with a Varian 400 spectrometer at 161.9 MHz. Solution mass spectra
were obtained with a Trace DSQ mass spectrometer in ESI mode
and a Trace quadrupole mass spectrometer in EI mode. High-resolu-
tion mass spectra were acquired with an Agilent 6210 TOF mass
3
4
Figure 2. X-ray crystal structure of (R)-3o.
On the basis of the experimental results[ and previous
10]
work,[
5,8,11]
a plausible mechanism and an activation model are
outlined in Scheme 4. The direct nucleophilic addition of the spectrometer. The enantiomeric excesses of the target molecules
chiral bifunctional ferrocenylphosphine catalyst to the MBH were determined through chiral-phase HPLC analysis with an
Eur. J. Org. Chem. 2016, 2139–2144
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Agilent 1100 HPLC system (Daicel Chiralcel AD-H, OD-H, or AS-H
acetate 1 (0.5 mmol), 2 (1.5 mmol, 220.5 mg), and chiral ferrocenyl-
column and eluted with n-hexane/iPrOH) with a UV diode array phosphine LB4 (59.1 mg, 0.1 mmol) was added anhydrous CHCl3
detector (DAD). The X-ray analysis was performed with Xcalibur and
Gemini instruments.
The MBH adducts 1 were prepared by the literature procedure.[15]
(2.5 mL). The reaction mixture stirred at room temperature under
an argon atmosphere for 120 h. The reaction was monitored by
TLC. After the starting substrates were consumed, the solvent was
removed under reduced pressure, and the residue was purified by
silica gel column chromatography (eluent: n-hexane/EtOAc/CH Cl
(
S)-5-Chloro-N-[1′-(R)-2′-(diphenylphosphanyl)ferrocenyl]ethyl-
thiophene-2-carboxamide (LB1): A mixture of 5-chlorothiophene-
-carboxylic acid (0.24 g, 1.5 mmol), bis(trichloromethyl)carbonate
0.22 g, 0.75 mmol), and N,N-dimethylformamide (DMF; 1.10 mg,
.015 mmol) in toluene (5 mL) was heated to 110 °C. Then, the
2
2
8:1:1) to give the corresponding amination adduct 3.
2
(
0
Sixteen chiral products were synthesized, of which 12 were new
compounds (3c, 3d–3f, 3h–3l, and 3n–3p).
generated 5-chlorothiophene-2-carbonyl chloride was cooled to
room temperature and added to a solution of (S)-1-(S)-[diphenyl-
(
(
S)-N-[2-Methoxycarbonyl-1-(4′-nitrophenyl)allyl]phthalimide
20
1
3a): Yellow oil. [α]D = –10.4 (c = 0.5, CHCl ). H NMR (400 MHz,
3
phosphinoferrocenyl]ethylamine (0.21 g, 0.50 mmol) in CH Cl2
2
CDCl ): δ = 8.21 (d, J = 8.4 Hz, 2 H), 7.84–7.87 (m, 2 H), 7.74–7.76
3
(5 mL), and the reaction mixture was stirred at 0 °C for 1 h. After
(m, 2 H), 7.61 (d, J = 8.4 Hz, 2 H), 6.63 (s, 1 H), 6.52 (s, 1 H), 5.67 (s,
the completion of the reaction, water was added to quench the
reaction. The reaction mixture was then filtered and extracted with
CH Cl (3 × 10 mL), and the combined organic extracts were dried
1
1
H), 3.73 (s, 3 H) ppm. MS (EI): m/z (%) = 366 (5), 334 (97), 147 (18),
04 (95), 76 (35). The ee was determined by HPLC with a chiral
2
2
OD-H column (λ = 218 nm; eluent: n-hexane/iPrOH 85:15; flow rate:
.8 mL/min; tmajor = 25.045 min, tminor = 32.678 min; ee = 96 %).
with Na SO , filtered, and concentrated. The residue was purified
2
4
0
by flash column chromatography to afford LB1 (0.24 g, 86 %) as a
2
0
1
(S)-N-[2-(Ethoxycarbonyl)-1-(4′-nitrophenyl)allyl]phthalimide
yellow solid, m.p. 118.5–120.5 °C. [α]D = +323.2 (c = 0.5, CHCl ). H
3
2
0
1
(3b): Yellow oil. [α] = +2.8 (c = 0.5, CHCl3). H NMR (400 MHz,
NMR (400 MHz, CDCl ): δ = 7.57–7.49 (m, 2 H), 7.40 (d, J = 5.2 Hz,
D
3
CDCl ): δ = 8.21 (d, J = 8.8 Hz, 2 H), 7.84–7.87 (m, 2 H), 7.74–7.76
3
H), 7.19 (d, J = 3.2 Hz, 5 H), 7.14 (s, 1 H), 6.99 (d, J = 3.6 Hz, 1 H),
.80 (d, J = 2.4 Hz, 1 H), 5.25 (q, J = 6.0 Hz, 1 H), 4.54 (s, 1 H), 4.36
3
(m, 2 H), 7.62 (d, J = 8.8 Hz, 2 H), 6.63 (d, J = 1.2 Hz, 1 H), 6.51 (s, 1
6
s, 1 H), 4.02 (s, 5 H), 3.86 (s, 1 H), 1.41 (d, J = 6.0 Hz, 3 H) ppm. 13
H), 5.63 (d, J = 1.6 Hz, 1 H), 4.21–4.12 (m, 2 H), 1.19 (t, J = 7.2 Hz, 3
H) ppm. MS (EI): m/z (%) = 380 (3), 334 (60), 306 (100), 104 (36), 76
(
C
NMR (100 MHz, CDCl ): δ = 159.0, 138.7, 138.0, 136.3, 135.0, 134.8,
3
(25). The ee was determined by HPLC with a chiral OD-H column
1
7
34.6, 132.6, 132.4, 129.4, 128.3 (2 C), 128.2, 126.7 (2 C), 95.7, 95.5,
3.9, 73.8, 72.2, 71.3, 70.0 (5 C), 69.6, 46.0, 23.0 ppm. 3 P NMR
1
(λ = 218 nm; eluent: n-hexane/iPrOH 85:15; flow rate: 0.8 mL/min;
tmajor = 19.380 min, tminor = 23.288 min; ee = 72 %).
(
5
+
162 MHz, CDCl , 85 % H PO ): δ = –23.73 ppm. MS (ESI): m/z (%) =
3 3 4
+
80.6 (100) [M + Na] . HRMS (ESI): calcd. for C H ClFeNNaOPS [M
2
9
25
(S)-N-[2-(Butoxycarbonyl)-1-(4′-nitrophenyl)allyl]phthalimide
+
Na] 580.0325; found 580.0322.
3c): Yellow oil. [α]D = –7.2 (c = 0.5, CHCl3). 1H NMR (400 MHz,
20
(
Catalyst LB2 was prepared as a yellow solid by a similar procedure.
CDCl ): δ = 8.18 (d, J = 7.2 Hz, 2 H), 7.83 (d, J = 2.4 Hz, 2 H), 7.73
3
2
0
[
α] = –328.0 (c = 0.5, CHCl3).
(d, J = 2.8 Hz, 2 H), 7.60 (d, J = 7.6 Hz, 2 H), 6.62 (s, 1 H), 6.50 (s, 1
H), 5.63 (s, 1 H), 4.12 (d, J = 5.6 Hz, 2 H), 1.57–1.54 (m, 2 H), 1.29–
D
(
R)-3-Methyl-N-[1′-(S)-2′-(diphenylphosphanyl)ferrocenyl]ethyl-
1
.26 (m, 2 H), 0.87 (t, J = 6.4 Hz, 3 H) ppm. 13C NMR (100 MHz,
thiazole-2-carboxamide (LB3): By following a similar procedure as
that for LB1, LB3 (0.24 g, 92 %) was obtained a yellow solid, m.p.
CDCl ): δ = 167.4 (2 C), 165.0, 147.6, 144.2, 136.7, 134.4 (2 C), 131.6,
3
2
0
1
129.7 (2 C), 129.4 (2 C), 123.7 (2 C), 123.6 (2 C), 65.4, 54.0, 30.7, 19.3,
5
8.8–60.8 °C. [α]D = –339.2 (c = 0.5, CHCl3). H NMR (400 MHz,
1
3.8 ppm. ES (EI): m/z (%): 408 (4), 334 (58), 306 (100), 104 (52), 76
CDCl ): δ = 8.63 (s, 1 H), 7.55–7.48 (m, 2 H), 7.38 (d, J = 5.2 Hz, 3
3
+
(20). HRMS (ESI): calcd. for C H N NaO [M + Na] 431.1214; found
22 20 2 6
H), 7.18–7.08 (m, 5 H), 6.71–6.62 (m, 1 H), 5.33 (q, J = 5.2 Hz, 1 H),
431.1226. The ee was determined by HPLC with a chiral OD-H col-
4
.53 (s, 1 H), 4.35 (t, J = 2.4 Hz, 1 H), 4.03 (s, 5 H), 3.88–3.81 (m, 1
1
3
umn (λ = 218 nm; eluent: n-hexane/iPrOH 85:15; flow rate: 0.8 mL/
min; tmajor = 15.775 min, tminor = 18.969 min; ee = 73 %).
H), 2.68 (s, 3 H), 1.45 (d, J = 6.8 Hz, 3 H) ppm. C NMR (100 MHz,
CDCl ): δ = 159.7, 155.8, 151.6, 138.8, 136.4, 135.0, 134.7, 132.4,
3
1
7
8
32.2, 129.3, 128.2, 128.2, 128.1, 125.9, 95.4, 95.1, 74.4, 74.3, 72.3,
1.0, 70.0 (5 C), 69.5, 45.9, 22.7, 17.5 ppm. P NMR (162 MHz, CDCl3,
(S)-N-[2-Methoxycarbonyl-1-(4′-fluorophenyl)allyl]phthalimide
3
1
20
1
(3d): Colorless oil. [α]D = +71.7 (c = 0.4, CHCl ). H NMR (400 MHz,
3
5 % H PO ): δ = –24.60 ppm. MS (ESI): m/z (%) = 561.2 (100) [M +
CDCl ): δ = 7.83 (m, 2 H), 7.71 (m, 2 H), 7.43 (m, 2 H), 7.01–7.05 (m,
3
4
3
+
+
Na] . HRMS (ESI): calcd. for C H FeN NaOPS [M + Na] 561.0823;
found 561.0845.
2 H), 6.56 (d, J = 1.6 Hz, 1 H), 6.38 (s, 1 H), 5.63 (d, J = 1.6 Hz, 1 H),
2
9
27
2
3.71 (s, 3 H) ppm. 13C NMR (100 MHz, CDCl ): δ = 167.6, 165.7, 163.4,
3
1
61.0, 137.3, 134.0 (2 C), 132.7, 131.6, 130.4 (2 C), 129.1 (2 C), 123.3
(
R)-4,5-Dichloro-N-[1′-(S)-2′-(diphenylphosphanyl)ferro-
(
(
2 C), 115.6, 115.4, 54.0, 52.2 ppm. MS (EI): m/z (%) = 339 (6), 306
80), 278 (72), 250 (100), 104 (38), 76 (35). HRMS (ESI): calcd. for
cenyl]ethylthiophene-2-carboxamide (LB4): By following a simi-
lar procedure as that for LB1, LB4 (0.26 g, 87 %) was obtained as a
yellow solid, m.p. 85.5–87.8 °C. [α] = –340.4 (c = 0.5, CHCl ). H
+
2
0
1
C H FNNaO [M + Na] 362.0799; found 362.0792. The ee was
19 14
4
D
3
determined by HPLC with a chiral OD-H column (λ = 220 nm; eluent:
n-hexane/iPrOH 75:25; flow rate: 0.8 mL/min; tmajor = 8.737 min,
tminor = 14.274 min; ee = 72 %).
NMR (400 MHz, CDCl ): δ = 7.54–7.47 (m, 2 H), 7.38 (d, J = 4.8 Hz,
3
3
H), 7.18 (d, J = 4.0 Hz, 5 H), 6.56 (s, 1 H), 6.54–6.49 (m, 1 H), 5.33
(
q, J = 6.8 Hz, 1 H), 4.53 (s, 1 H), 4.35 (t, J = 2.4 Hz, 1 H), 4.03 (s, 5
13
H), 3.87–3.83 (m, 1 H), 1.47 (d, J = 6.4 Hz, 3 H) ppm. C NMR
100 MHz, CDCl ): δ = 158.1, 138.9, 136.2, 135.8, 134.9, 134.7, 132.6,
(
R)-N-[2-Methoxycarbonyl-1-(2′-chlorophenyl)allyl]phthalimide
(
20
1
3
(3e): Colorless oil. [α]D = –9.0 (c = 0.2, CHCl ). H NMR (400 MHz,
3
1
7
32.4, 129.4, 129.3, 128.5, 128.3, 128.2, 126.1, 123.9, 94.8, 94.6, 74.8,
4.7, 72.4, 70.9, 70.1 (5 C), 69.6, 46.1, 21.9 ppm. P NMR (162 MHz,
CDCl ): δ = 7.84–7.86 (m, 2 H), 7.73–7.76 (m, 2 H), 7.51–7.53 (m, 1
3
3
1
H), 7.38–7.40 (m, 1 H), 7.27–7.29 (m, 2 H), 6.77 (s, 1 H), 6.60 (s, 1 H),
CDCl , 85 % H PO ): δ = –24.67 ppm. MS (ESI): m/z (%) = 630.5 (100)
13
3
3
4
5.62 (s, 1 H), 3.73 (s, 3 H) ppm. C NMR (100 MHz, CDCl ): δ = 167.6
3
+
+
[
M + K] . HRMS (ESI): calcd. for C H Cl FeNOPS [M + K] 613.9936;
29 24 2
(2 C), 165.6, 136.2, 134.4, 134.2 (2 C), 133.6, 131.6 (2 C), 130.2, 129.7,
found 613.9951.
129.5, 128.8, 126.7, 123.5 (2 C), 52.4, 52.2 ppm. MS (EI): m/z (%) =
General Procedure for the Enantioselective Allylic Substitution:
To a flame-dried Schlenk tube charged with the corresponding MBH
355 (1), 319 (100), 288 (32), 260 (19), 104 (16), 76 (10). HRMS (ESI):
+
calcd. for C H ClNNaO [M + Na] 378.0504; found 378.0518. The
19
14
4
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© 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

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ee was determined by HPLC with a chiral OJ-H column (λ = 220 nm;
eluent: n-hexane/iPrOH 85:15; flow rate: 0.8 mL/min; tmajor
3.296 min, tminor = 26.925 min; ee = 90 %).
(400 MHz, CDCl ): δ = 7.81–7.83 (m, 2 H), 7.68–7.70 (m, 2 H), 7.17–
3
=
7.18 (m, 2 H), 7.10 (d, J = 8.4 Hz, 1 H), 6.54 (d, J = 1.2 Hz, 1 H), 6.33
1
3
3
(s, 1 H), 5.66 (d, J = 1.6 Hz, 1 H), 3.71 (s, 3 H), 2.24 (s, 6 H) ppm.
C
NMR (100 MHz, CDCl ): δ = 167.3 (2 C), 165.5, 137.3, 136.4, 136.1,
3
(
(
S)-N-[2-Methoxycarbonyl-1-(3′-chlorophenyl)allyl]phthalimide
1
5
2
+
34.0, 133.6 (2 C), 131.5 (2 C), 129.5 (2 C), 129.0, 125.8, 123.1 (2 C),
4.8, 52.5, 20.5, 20.1 ppm. MS (EI): m/z (%) = 349 (11), 289 (100),
60 (83), 232 (10), 104 (49). HRMS (ESI): calcd. for C H NNaO [M
3f): Colorless oil. [α] D2 0 = +73.3 (c = 0.15, CHCl ). H NMR (400 MHz,
1
3
CDCl ): δ = 7.83–7.85 (m, 2 H), 7.72–7.73 (m, 2 H), 7.42 (s, 1 H), 7.28–
7
ppm. C NMR (100 MHz, CDCl ): δ = 167.7 (2 C), 165.8, 139.0, 137.0,
3
21
19
4
.32 (m, 3 H), 6.59 (s, 1 H), 6.37 (s, 1 H), 5.65 (s, 1 H), 3.71 (s, 3 H)
+
Na] 372.1206; found 372.1211. The ee was determined by HPLC
13
3
with a chiral OD-H column (λ = 220 nm; eluent: n-hexane/iPrOH
5:15; flow rate: 0.6 mL/min; tmajor = 16.840 min, tminor = 21.436 min;
1
(
2
34.6, 134.2 (2 C), 131.7, 129.9 (2 C), 129.8, 128.8, 128.4, 126.9, 123.6
2 C), 54.3, 52.5 ppm. MS (EI): m/z (%) = 355 (13), 295 (88), 267 (36),
07 (100), 104 (70), 76 (45). HRMS (ESI): calcd. for C H ClNNaO
8
ee = 91 %).
1
9
14
4
+
[
M + Na] 378.0504; found 378.0514. The ee was determined by
HPLC with a chiral OJ-H column (λ = 220 nm; eluent: n-hexane/
iPrOH 95:5; flow rate: 0.8 mL/min; tmajor = 34.998 min, tminor
2.733 min; ee = 82 %).
(S)-N-[2-Methoxycarbonyl-1-(4′-methoxyphenyl)allyl]phthal-
2
0
1
imide (3l): Colorless oil. [α] = +78.7 (c = 0.5, CHCl3). H NMR
D
=
(400 MHz, CDCl ): δ = 7.80–7.82 (m, 2 H), 7.68–7.70 (m, 2 H), 7.38
3
3
(d, J = 8.4 Hz, 2 H), 6.87 (d, J = 8.4 Hz, 2 H), 6.54 (d, J = 1.6 Hz, 1
H), 6.34 (s, 1 H), 5.65 (d, J = 2.0 Hz, 1 H), 3.81 (s, 3 H), 3.72 (s, 3 H)
(
(
S)-N-[2-Methoxycarbonyl-1-(4′-chlorophenyl)allyl]phthalimide
ppm. 13C NMR (100 MHz, CDCl
): δ = 167.8 (2 C), 166.0, 159.3, 137.9,
34.0 (2 C), 131.9, 130.0 (3 C), 129.1 (2 C), 123.4 (2 C), 114.0 (2 C),
3g): Colorless oil. [α]2 = +74.7 (c = 0.8, CHCl ). H NMR (400 MHz,
0
1
3
D
3
1
5
2
CDCl ): δ = 7.82–7.84 (m, 2 H), 7.70–7.73 (m, 2 H), 7.30–7.39 (m, 4
H), 6.57 (d, J = 1.6 Hz, 1 H), 6.37 (s, 1 H), 5.64 (d, J = 1.6 Hz, 1 H),
3
5.4, 54.4, 52.3 ppm. MS (EI): m/z (%) = 351 (13), 291 (100), 290 (57),
62 (32), 104 (41), 76 (29). HRMS (ESI): calcd. for C H NNaO [M +
20
17
5
3
(
.71 (s, 3 H) ppm. MS (EI): m/z (%) = 355 (5), 325 (15), 297 (20), 295
100), 104 (33), 50 (2). Th ee was determined by HPLC with a chiral
OD-H column (λ = 220 nm; eluent: n-hexane/iPrOH 85:15; flow rate:
.6 mL/min; tmajor = 13.926 min, tminor = 19.816 min; ee = 75 %).
+
Na] 374.0999; found 374.1007. The ee was determined by HPLC
with a chiral OD-H column (λ = 218 nm; eluent: n-hexane/iPrOH
85:15; flow rate: 0.8 mL/min; tmajor = 22.411 min, tminor = 17.828 min;
0
ee = 62 %).
(
(
S)-N-[2-Methoxycarbonyl-1-(4′-bromophenyl)allyl]phthalimide
3h): Colorless oil. [α]2 = +38.3 (c = 1.0, CHCl ). H NMR (400 MHz,
0
1
(S)-N-[(2-Methoxycarbonyl-1-phenyl)allyl]phthalimide (3m): Yel-
D
3
2
0
1
low oil. [α] = +82.4 (c = 0.5, CHCl ). H NMR (400 MHz, CDCl ): δ =
CDCl ): δ = 7.82–7.84 (m, 2 H), 7.70–7.72 (m, 2 H), 7.47 (d, J = 8.4 Hz,
2
5
CDCl ): δ = 167.7 (2 C), 165.8, 137.1, 136.0, 134.2 (2 C), 131. 8 (2 C),
1
D
3
3
3
7.82–7.84 (m, 2 H), 7.69–7.71 (m, 2 H), 7.30–7.44 (m, 5 H), 6.56 (d,
H), 7.32 (d, J = 8.4 Hz, 2 H), 6.57 (d, J = 0.8 Hz, 1 H), 6.36 (s, 1 H),
1
3
J = 1.6 Hz, 1 H), 6.39 (s, 1 H), 5.63 (d, J = 1.6 Hz, 1 H), 3.71 (s, 3 H)
ppm. MS (EI): m/z (%) = 321 (2), 289 (33), 261 (100), 104 (26), 76
.64 (d, J = 1.6 Hz, 1 H), 3.71 (s, 3 H) ppm. C NMR (100 MHz,
3
(
(
10). The ee was determined by HPLC with a chiral OD-H column
λ = 220 nm; eluent: n-hexane/iPrOH 70:30; flow rate: 0.8 mL/min;
31.7, 130.4 (2 C), 129.5 (2 C), 123.5 (2 C), 122.3, 54.2, 52.5 ppm. MS
(
(
EI): m/z (%) = 399 (7), 339 (96), 311 (26), 104 (66), 76 (100). HRMS
ESI): calcd. for C H BrNNaO [M + Na] 421.9998; found 422.0004.
+
tmajor = 10.306 min, tminor = 24.835 min; ee = 92 %).
19
14
4
The ee was determined by HPLC with a chiral OD-H column (λ =
20 nm; eluent: n-hexane/iPrOH 85:15; flow rate: 0.8 mL/min;
tmajor = 10.880 min, tminor = 14.623 min; ee = 73 %).
(
S)-N-[2-Methoxycarbonyl-1-(4′-trifluoromethylphenyl)allyl]-
2
20
phthalimide (3n): White solid; m.p. 80.2–81.0 °C. [α] = +77.2 (c =
0.5, CHCl ). H NMR (400 MHz, CDCl ): δ = 7.83–7.85 (m, 2 H), 7.71–
D
1
3
3
7
.73 (m, 2 H), 7.58 (dd, J = 18.8, 8.4 Hz, 4 H), 6.60 (s, 1 H), 6.47 (s, 1
(
(
S)-N-[2-Methoxycarbonyl-1-(3′-bromophenyl)allyl]phthalimide
13
2
0
1
H), 5.64 (s, 1 H), 3.72 (s, 3 H) ppm. C NMR (100 MHz, CDCl ): δ =
3i): Colorless oil. [α] = +89.2 (c = 0.5, CHCl ). H NMR (400 MHz,
3
D
3
1
(
67.6 (2 C), 165.7, 140.9, 136.9, 134.3 (2 C), 131.7, 129.7 (2 C), 129.1
3 C), 125.6 (3 C), 123.6 (2 C), 54.3, 52.5 ppm. MS (EI): m/z (%) =
389 (4), 328 (100), 300 (51), 104 (76), 76 (47). HRMS (ESI): calcd. for
CDCl ): δ = 7.82–7.84 (m, 2 H), 7.70–7.72 (m, 2 H), 7.57 (s, 1 H), 7.36–
3
7
1
1
1
3
.44 (m, 2 H), 7.20–7.24 (m, 1 H), 6.59 (s, 1 H), 6.36 (s, 1 H), 5.66 (s,
1
3
H), 3.73 (s, 3 H) ppm. C NMR (100 MHz, CDCl ): δ = 167.0 (2 C),
3
+
C H F NNaO [M + Na] 412.0767; found 412.0769. The ee was
65.1, 138.8, 136.5, 133.8 (2 C), 131.3 (2 C), 130.9 (2 C), 129.8, 129.4,
27.0, 123.2 (2 C), 122.4, 54.3, 52.6 ppm. MS (EI): m/z (%) = 399 (6),
69 (28), 341 (42), 231 (100), 104 (66), 76 (42). HRMS (ESI): calcd. for
20 14
3
4
determined by HPLC with a chiral OD-H column (λ = 222 nm; eluent:
n-hexane/iPrOH 85:15; flow rate: 0.8 mL/min; tmajor = 9.544 min,
tminor = 10.887 min; ee = 89 %).
C H BrNNaO [M + Na]+ 421.9998; found 422.0015. The ee was
19
14
4
determined by HPLC with a chiral OJ-H column (λ = 220 nm; eluent:
n-hexane/iPrOH 98:2; flow rate: 0.8 mL/min; tmajor = 60.731 min,
tminor = 55.895 min; ee = 89 %).
(
R)-N-[2-Methoxycarbonyl-1-(2,4-dichlorophenyl)allyl]-phthal-
20
imide (3o): White solid; m.p. 105.1–106.0 °C. [α] = –52.6 (c = 1.0,
CHCl ). H NMR (400 MHz, CDCl ): δ = 7.83–7.85 (m, 2 H), 7.72–7.74
D
1
3
3
(
(
S)-N-[2-Methoxycarbonyl-1-(4′-methylphenyl)allyl]phthalimide (m, 2 H), 7.46 (d, J = 8.4 Hz, 1 H), 7.39 (d, J = 2.4 Hz, 1 H), 7.23–7.25
3j): Colorless oil. [α] D2 0 = +76.5 (c = 0.5, CHCl ). H NMR (400 MHz, (m, 1 H), 6.70 (s, 1 H), 6.59 (d, J = 1.2 Hz, 1 H), 5.64 (d, J = 1.6 Hz, 1
1
3
CDCl ): δ = 7.80–7.83 (m, 2 H), 7.68–7.71 (m, 2 H), 7.32 (d, J = 8.0 Hz, H), 3.72 (s, 3 H) ppm. 13C NMR (100 MHz, CDCl
): δ = 166.9 (2 C),
164.8, 135.7, 134.4, 134.1, 133.9 (2 C), 132.6, 131.2 (2 C), 131.0, 129.2,
3
3
2
H), 7.15 (d, J = 8.0 Hz, 2 H), 6.55 (d, J = 1.6 Hz, 1 H), 6.36 (s, 1 H),
5
.66 (d, J = 1.6 Hz, 1 H), 3.73 (s, 3 H), 2.37 (s, 3 H) ppm. 13C NMR
128.4, 126.7, 123.3 (2 C), 52.7, 51.9 ppm. MS (EI): m/z (%) = 355 (75),
(
1
100 MHz, CDCl ): δ = 167.8 (2 C), 166.1, 137.9, 137.7, 134.0 (2 C),
31.9 (3 C), 129.3 (3 C), 128.6 (2 C), 123.4 (2 C), 54.7, 52.4, 21.4 ppm.
266 (40), 206 (11), 73 (100), 59 (5). HRMS (ESI): calcd. for
3
+
C
19
H14Cl
NO
[M + H] 390.0294; found 390.0284. The ee was deter-
2
4
MS (EI): m/z (%) = 335 (5), 304 (9), 276 (15), 275 (100), 76 (27). HRMS
mined by HPLC with a chiral OD-H column (λ = 220 nm; eluent:
ESI): calcd. for C H NNaO [M + Na] 358.1050; found 358.1064. n-hexane/iPrOH 85:15; flow rate: 0.8 mL/min; tmajor = 11.435 min,
+
(
20
17
4
The ee was determined by HPLC with a chiral OD-H column (λ =
18 nm; eluent: n-hexane/iPrOH 85:15; flow rate: 0.8 mL/min;
tmajor = 12.303 min, tminor = 14.144 min; ee = 73 %).
t
minor = 23.534 min; ee = 94 %).
2
(
S)-N-[(2-Methoxycarbonyl-1-naphthyl)allyl]phthalimide (3p):
20
1
Colorless oil. [α]D = +52.7 (c = 0.4, CHCl ). H NMR (400 MHz, CDCl ):
3
3
(
S)-N-[2-Methoxycarbonyl-1-(3,4-dimethylphenyl)allyl]phthal- δ = 7.98 (d, J = 8.4 Hz, 1 H), 7.82–7.88 (m, 4 H), 7.69–7.72 (m, 2 H),
imide (3k): Colorless oil. [α]D = +21.2 (c = 0.2, CHCl3). 1H NMR 7.64 (d, J = 7.2 Hz, 1 H), 7.44–7.55 (m, 3 H), 7.23 (s, 1 H), 6.59 (d, J =
20
Eur. J. Org. Chem. 2016, 2139–2144
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2143 © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

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0
(
1
1
.8 Hz, 1 H), 5.63 (d, J = 1.6 Hz, 1 H), 3.72 (s, 3 H) ppm. 13C NMR
100 MHz, CDCl ): δ = 167.9 (2 C), 166.0, 137.1, 134.1 (2 C), 133.8,
32.0, 131.7, 130.9, 129.4 (2 C), 129.0 (2 C), 126.9, 126.8, 125.7, 125.1,
k) X.-Y. Han, Y.-Q. Wang, F.-R. Zhong, Y.-X. Lu, Org. Biomol. Chem. 2011, 9,
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7429–7438; m) G. Martelli, M. Orena, S. Rinaldi, Eur. J. Org. Chem. 2012,
4140–4152; n) Y. Wei, M. Shi, Chem. Rev. 2013, 113, 6659–6690; o) F.-L.
3
23.5 (2 C), 123.1, 52.5, 51.5 ppm. MS (EI): m/z (%) = 355 (3), 327
Hu, M. Shi, Org. Chem. Front. 2014, 1, 587–595; p) Y.-N. Gao, Q. Xu, M.
Shi, ACS Catal. 2015, 5, 6608–6614.
(
[
6), 207 (100), 165 (87), 104 (25). HRMS (ESI): calcd. for C H NNaO
M + Na] 394.1050; found 394.1048. The ee was determined by
23 17 4
+
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iPrOH 90:10; flow rate: 1.0 mL/min; tmajor = 25.194 min, tminor
3.630 min; ee = 78 %).
=
2
Supporting Information (see footnote on the first page of this
article): Spectroscopic data and chiral HPLC traces of the com-
pounds shown in Tables 1 and 2, X-ray crystallographic data for 3o,
and detailed descriptions of the experimental procedures.
Acknowledgments
The authors thank the National Natural Science Foundation of
China (NSFC) (grant number 21276238) for financial support.
1
, 1152–1156; m) P. Putaj, I. Ticha, I. Cisarova, J. Vesely, Eur. J. Org. Chem.
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Keywords: Asymmetric catalysis · Amination · Phosphanes ·
Configuration determination
[
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[10] The absolute configuration of 3o was determined to be R by X-ray analy-
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S according to their specific rotation (see the Supporting Information).
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Received: January 12, 2016
Published Online: April 6, 2016
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2144
© 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim